UV-reflective interference layer system

ABSTRACT

There is provided a UV-reflective interference layer system for transparent substrates with broadband anti-reflection properties in the visible wavelength range. The interference layer system includes at least four individual layers. Successive layers have different refractive indices and the individual layers contain UV and temperature-stable inorganic materials.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation-in-part of (a) U.S. patentapplication Ser. No. 09/514,437, which was filed on Feb. 28, 2000, and(b) International Patent Application PCT/EP00/12878, which was filedDec. 15, 2000. The present application is also claiming priority ofGerman Patent Application DE 199 62 144.6, filed Dec. 22, 1999.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention concerns a UV-reflective interference layer system fortransparent substrates with broadband antireflection in the visiblewavelength range, a method for coating a substrate with such a layersystem, and the use of such coating systems in various fields ofapplication.

2. Description of the Prior Art

Currently known glass antireflections for the visible spectral range,such as the MIROGARD or the AMIRAN antireflection of Schott-DESAG AG,Grünenplan, are interference filters of three layers, wherein a layerwith an intermediate index of refraction is first deposited, followed bya layer with high index of refraction, usually TiO₂, and then a layerwith low index of refraction, usually SiO₂ or MgF₂. As the layer withintermediate index of refraction, for example, a mixture of SiO₂ andTiO₂, but also Al₂O₃ is used. Such three-layer antireflections aredeposited, for example, on eyeglass lenses, on monitors, on plate glass,such as display window panels, on treated lenses, etc.

In most instances, these filters have a blue-violet or green residualreflection. When light impinges perpendicularly, the reflectioncharacteristic of glasses coated on both sides is characterized in thatthe reflection within the wavelength interval of around 400-700 nm isless than 1%, for example, but outside this range the reflection risesto values of up to around 30% (V or W-shaped characteristic), i.e., farabove the 8% of uncoated glass.

The drawback to such systems is that, when viewing at an angle thatincreasingly deviates from the perpendicular, the characteristic shiftsto ever shorter wavelengths, so that the long-wave reflection maximumends up in the visible range, and produces an undesirable red componentto the reflected light color.

One goal of the present invention is therefore to find an antireflectionwhose residual reflection is low in a much broader wavelength range,i.e., in the range from 400 to at least 800 nm with perpendicularincidence of light, and which furthermore also provides broadbandantireflection at rather large viewing angles. In many applications,such as display window glazings or glazings for pictures, aneutral-color appearance is in fact desirable, especially for differentviewing angles.

Especially for picture glazings, say, in museums, but also in the caseof display window glazings, furthermore, it is desirable that anantireflecting glass—if possible, color-neutral—at the same timeprovides the function of protecting the colors of the picture or thenatural or synthetic fibers, as well as the dyestuffs of the windowdisplays, against ultraviolet light.

As is known, the UV component of sunlight or that of lamp light,especially in the case of metal halide or other gas discharge lamps, butalso even with halogen bulbs, is sufficient to cause considerable damageover a lengthy period of time, such as discoloration or embrittlement ofnatural or synthetic fabrics. A UV protection would also be desirablefor glazings in office or residential buildings, in order to greatlyreduce the fading of wood surfaces, draperies, upholstered furniture,etc., under direct sunlight, and thus enable, for example, an improvedpassive utilization of solar energy. Present-day thermal protectionglasses, which contain a thin silver layer, are not antireflective inthe visible range, and furthermore also do not offer sufficient UVprotection, since thin silver layers become transparent in the UV.

In the case of known antireflective soft glass, UV protection isachieved by the use of organic polymers as absorbers of UV light, forexample, as compound glass, wherein two glass panes are laminatedtogether with a PVB plastic foil adapted by its index of refraction tothe glass, for example, 380 μm in thickness (the glass MIROGARD-PROTECTfrom Schott-DESAG). Such glasses are [used] under intense lamp light,for example, as front panels for lamps, but they are nottemperature-stable and they are also degraded by intensive UV radiation.Also, their three-layer antireflection on one side has theabove-mentioned limitations, and furthermore the production of compoundglass is costly.

Another possibility is the use of UV-absorbing varnish layers, which areseveral micrometers thick and are transparent to visible light. Suchvarnish layers are likewise not stable to UV and temperature, and afterbeing deposited on the glass they must further be made antireflective.Regarding the state of the art, refer also to the followingpublications:

D1: H. Schröder, “Oxide Layers Deposited from Organic Solutions”, inPhysics of Thin Films, Academic Press, New York, London, Vol. 5 (1969),pp. 87-140

D2: H. Schröder, Optica Acta 9, 249 (1962)

D3: W. Geffeken, Glastech. Ber. 24, p. 143 (1951)

D4: H. Dislich, E. Hussmann, Thin Solid films 77 (1981), pp. 129-139

D5: N. Arfsten, R. Kaufmann, H. Dislich, Patent DE 3300589 C2

D6: N. Arfsten, B. Lintner, et al., Patent DE 4326947 C1

D7: A. Pein, European Patent 0 438 646 B1

D8: I. Brock, G. Frank, B. Vitt, European Patent 0 300 579 A2

D9: Kienel/Frey (ed.), “Dünnschicht-Technologie [Thin layertechnology]”, VDI-Verlag, Düsseldorf (1987)

D10: R. A. Häfer, “Oberflächen- und Dünnschicht-Technologie [Surface andthin layer technology]”, Part I, “Coating of Surfaces”, Springer-Verlag(1987)

whose disclosure contents are fully incorporated in the presentapplication.

SUMMARY OF THE INVENTION

The object of the invention is to specify a coating for a transparentsubstrate, especially glasses, with which the above-describeddisadvantages can be overcome.

In particular, one should achieve a UV filtering, on the one hand,without the use of UV or temperature-unstable polymer foils or varnish,and, on the other hand, the antireflection of visible light should bemuch more broadband and color neutral at the same time.

As regards the UV filtering, one should achieve approximately the samecharacteristics as for foil or varnish systems.

According to the invention, the object is solved by an interferencelayer system that comprises at least four individual layers, wherein theconsecutive layers have different indices of refraction and theindividual layers comprise UV and temperature-stable inorganicmaterials.

Especially preferred is an interference layer system of five layers withthe structure: glass +M1/T1/M2/T2/S, wherein the high-refractingmaterial T has an index of refraction in the range of 1.9-2.3 at awavelength of 550 nm, the low-refracting material S has an index ofrefraction between 1.38 and 1.50, and the intermediate-refractingmaterial M has an index of refraction in the range of 1.6-1.8, withlayer thicknesses of the individual materials in the ranges of 70 to 100nm (M1), 30 to 70 nm (T1), 20 to 40 nm (M2), 30 to 50 nm (T2), and 90 to110 nm (S).

In one embodiment of the invention the highly refractive material istitanium dioxide, the low-refracting material is silicon dioxide, andthe intermediate-refracting material is a mixture of these substances.

In an alternative embodiment, instead of titanium dioxide one can alsouse niobium oxide Nb₂O₅, tantalum oxide Ta₂O₅, cerium oxide CeO₂,hafnium oxide HfO₂, as well as mixtures thereof with titanium dioxide orwith each other, as the high-refractive layers; instead of silicondioxide one can also use magnesium fluoride MgF₂ as the low-refractivelayer; and instead of Ti—Si oxide mixtures one can also use aluminumoxide Al₂O₃ or zirconium oxide ZrO₂ as the intermediate-refractivelayers.

As the transparent substrate, in a first embodiment, one can use softglass in the form of float glass, including a low-iron form.

As an alternative to this, one can also use hard glasses as thesubstrate, especially aluminosilicate and borosilicate hard glasses orquartz glass.

Besides the interference layer system, the invention also provides amethod for applying it onto a substrate.

In a first embodiment of the invention, the individual layers aredeposited by means of the dip method or the spin method of sol-geltechniques.

As an alternative to this, the layers can be deposited by cathodesputtering (for example), by physical vaporization, or by chemicalgas-phase deposition, especially plasma-supported.

Especially preferred, the interference coatings according to theinvention are deposited on transparent substrates comprising aninfrared-reflecting thermal protection coating, or transparent layerscomprising an interference layer system according to the invention areprovided with a thermal protection layer, so that a UV-reflectivethermal protection glass is obtained.

Thermal protection glasses are based on the principle of reflection ofthe infrared heat radiation by a thin, electrically conductive coatingthat is largely transparent in the visible range. Basically, tin oxideand silver-based layers are considered as heat-reflecting coatings.

Tin oxide can be deposited immediately after the float glassproduction—and application of a diffusion-inhibiting SiOx preliminarycoating—in the cool-down phase at around 600° C. by means of a sprayprocess. By doping with fluorine or antimony, surface resistances up to15 Ohms for a layer thickness of around 300 nm are achieved, so that amore than 80% degree of infrared reflection averaged out over thedistribution of 300 K thermal radiation is achieved.

As window glazing, therefore, this glass reflects back the majority ofthe thermal radiation into the space of a building.

The tin oxide deposited by spray pyrolysis during float glass productionof interior double-pane glass, for example, must be protected againstcleaning, even though it has good mechanical and chemical stability,since substances get worn down due to the relatively high roughness andhardness applied during cleaning processes, and drying is madedifficult.

In the double-pane insulated glass composite with an uncoated flat glasspane, these glasses achieve a heat transfer value—depending on the gasfilling and the glass spacing—of up to k=1.6 W/m²K. The drawback is theonly moderate visible transmission of 75% of such a double-paneinsulated glass for two panes with thickness of 4 mm, which ispredominantly attributable to the reflection at the boundary layers. TheUV transmission, which should be as low as possible not only when usedas glazing for museums or textile shops, but also for residential oroffice buildings, is 35% in the range of 280 to 380 nm.

Instead of doped tin oxide SnO₂:F,Sb, one can also use the transparentsemiconductor materials zinc oxide ZnO:Al (aluminum-doped) and indiumoxide In₂O₃:Sn (tin-doped, “ITO”). Although ITO has a considerably lowerelectrochemical stability than tin oxide and requires further treatmentsafter the spraying process, zinc oxide cannot be produced withsufficient electrical conductivity by means of a spray process.

Silver-based heat-reflecting coatings achieve significantly morefavorable surface resistances down to less than 1 Ohm and, thus,infrared emission levels of 9 to 4%, at the limit down to 2%, so thatk-values of 1.1 to 1.4 W/m²K are possible on the basis of such a coatedpane in the double-pane insulated glass compound. The visibletransmission in this case is at most 76% and if the silver layers arethicker it drops to around 68% for k-values below 1.0 W/m²K. The UVtransmission is 36-19%.

The deposition of silver layers is more favorable in terms of thermalreflection, but after the glass production it must be conducted bycostly vacuum coating methods, and furthermore additional dielectriclayers surrounding the silver layer on both sides and possibly alsometal layers to improve the transmission and the long-term stability arerequired.

A further drawback is that the silver layer composite can only be usedon the inside of double-pane insulated glasses, since there is nopermanent mechanical or even chemical stability with respect to cleaningprocesses.

The visible transmission of heat-reflecting insulated glasses, asdescribed above, is inadequate both in the case of tin oxide and forsilver-based layers. With an antireflection coating on all four boundarysurfaces of a double-pane insulated glass one can obtain glasses whosevisible transmission is boosted to 88%. However, the UV transmission isstill 25%.

By applying an interference layer system according to the invention, onecan obtain thermal protection glasses with low transmission in the UVrange and high transmission in the visible range, so-calledUV-reflective thermal protection glasses.

Preferably, a UV-reflective thermal protection glass according to theinvention comprises an infrared-reflecting thermal protection plateglass, coated with electrically conductive tin oxide, being provided onboth sides with a UV-reflective interference layer system, a single panethat is coated on one side with tin oxide and then provided on bothsides with the UV-reflective, broadband antireflecting multilayercoating [has] a (mean) visible transmission of 90% or more, as well as aUV transmission (280-380 nm) of 8% or less, while the thermal radiationproperties of the tin oxide remain unchanged.

As an alternative to this, UV-reflective thermal protection glasses canbe obtained with silver-based, heat-reflecting “low-e” layers,especially in the form of double-pane insulated glasses. If all theother three glass surfaces except the low-e layer applied to the insideof a glass surface are provided with an interference layer system, thevisible transmission increases, for example, from 76% to 85%—forunchanged heat-transfer value k—while the UV transmission is reducedfrom approximately 30% to around 4%.

If the low-e layer is applied on one side of a plate glass previouslymade antireflecting on both sides with an interference layer systemaccording to the invention, and combined with a second pane madeantireflecting on both sides with an interference layer system as adouble-pane insulating glass, the visible transmission is furtherincreased to 87%, while the UV transmission is reduced to 3%.

If the second pane is coated on one side with tin oxide prior to makingboth sides antireflecting with an interference layer system, the k-valuewill be reduced by around 0.2 W/m²K, i.e., from 1.0 to 0.8 W/m²K, forexample.

The visible transmission of a single pane coated with tin oxide on oneside and made antireflecting with an interference layer system on bothsides, having a thickness of 4 mm, is 10% higher in absolute terms thanthat of tin oxide thermal protection glass not made antireflecting, and2 to 3% higher than that of uncoated float glass. At the same time, theUV transmission is lowered from approximately 45% to 8% withoutapplication of polymer varnish or foil.

If one combines a tin oxide-coated single pane provided with theUV-reflective interference layer system on both sides with an identicalsecond pane, the remaining UV transmission will be lowered to 3%, andonly a small residue of long-wave radiation will still be admitted inthe wavelength region of 360 to 380 nm.

At the same time, the thermal protection properties are significantlyimproved by the infrared reflection now at two tin oxide layers, andk-values of around 1.2 W/m²K are possible, such as are otherwiseachieved only with silver-based thermal protection glasses. Theapplication of a double, IR-reflecting tin oxide layer is only possiblebecause, thanks to the efficient broadband antireflection of all fourboundary surfaces with an interference layer system according to theinvention, the total visible transmission is around 87% for normaliron-containing float glass with two panes of 4 mm thickness each.

If—as has been customary thus far—only one layer of tin oxide is used ina double-pane thermal protection glass, the k-value remains at theminimal 1.6 W/m²K, associated with a somewhat higher visibletransmission of 88% and a UV transmission of 4%.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention shall now be described more closely by means of thefigures.

These show:

FIG. 1 the degree of reflection plotted against the wavelength as afunction of the angle of incidence of the MIROGARD antireflection ofSCHOTT-DESAG, Grünenplan, according to the state of the art

FIG. 2 the degree of reflection plotted against the wavelength as afunction of the angle of incidence of the AMIRAN antireflection ofSCHOTT-DESAG, Grünenplan, according to the state of the art

FIG. 3 the transmissibility of UV filters on soft glass according to thestate of the art, as a function of wavelength

FIG. 4 the transmission spectrum of a system according to the inventionaccording to Example of embodiment 1

FIG. 5 the transmission spectrum of a system according to Example ofembodiment 1 with several panes

FIG. 6 reflection characteristic of a system according to the invention

FIG. 7 reflection characteristic of a system according to the inventionwith an angle of incidence of Φ=30°

FIGS. 8a, 8 b reflection characteristic of a system according to theinvention for an angle of incidence Φ=8°

FIG. 9 reflection characteristic of a system according to the inventionaccording to Example 2

FIG. 10 reflection characteristic of a system according to the inventionaccording to Example 3

FIGS. 11a-11 c schematic representation of various thermal protectionglasses

FIGS. 12a-12 c transmission characteristic of thermal protection glassesaccording to Example 4

FIGS. 12d-12 e reflection characteristic of thermal protection glassesaccording to Example 4

DESCRIPTION OF THE INVENTION

FIG. 1 shows the dependence of the degree of reflection R on the angleof incidence for the MIROGARD antireflection of Schott-DESAG. Themeasurements of the degree of reflection were plotted for various angles(12.5 to 50°) of the incident light vs. the normal line to the surface.

FIG. 2 shows the degree of reflection R for the three-layer AMIRANantireflections of Schott-DESAG AG, Grünenplan.

The systems according to FIGS. 1 and 2 show a strong dependence of thedegree of reflection on the angle of incidence of the light.

FIG. 3 shows the transmissibility of various UV filters according to thestate of the art on soft glass as a function of wavelength. Normalwindow glass is practically nontransmissible below 290 nm, because ofabsorption, so that only an improved blocking in the UV-B region, i.e.,to 315 nm, and primarily the blocking at 315 and 380 nm remains as aproblem.

A MIROGARD three-layer antireflection without plastic foil alreadyprovides a slight improvement in the UV blocking by absorption andreflection as compared to uncoated glass. MIROGARD-Protect compoundglass is very effective as a UV-A blocker, as are TrueVue and Sky Glas,but TrueVue is very blue in reflection and significantly yellow intransmission.

Examples 1-3 of a system according to the invention with properties thatare improved compared to the prior art shall now be described in detail:

EXAMPLE 1

(Color-neutral Filter):

A UV filter with combined broadband antireflecting action is produced onboth sides of soft glass (d=3 mm, not iron-poor) by the dip method(sol-gel process), for the purpose of the most color-neutral appearance.

The coatings on both sides each consist of five individual layers andpossess the structure: glass+M*+T+M+S. The individual layers are appliedidentically on both sides in a dipping step.

The layers designated T contain titanium dioxide TiO₂, the cover layerdesignated S contains silicon dioxide SiO₂, and the M layers are eachdrawn from mixed S and T solutions.

The float glass substrate is carefully cleaned prior to the coating. Thedip solutions are each applied in climate-controlled rooms of 28° C.with humidity of 7 to 12 g/m³, the drawing speeds for the individuallayers M*/T/M/T/S being: 495/262/345/206/498 mm/min.

The drawing of each gel layer is followed by a baking in air. The bakingtemperatures and times are 180° C./20 min. after production of thefirst, second and third gel layers and 440° C./30 min. after the fourthand fifth layers.

In the case of the T layers, the dip solution (per liter) is composedof:

68 ml of titanium-n-butylate, 918 ml of ethanol (abs.), 5 ml ofacetylacetone, and 9 ml of ethyl-butyrylacetate.

The dip solution for production of the S layer contains:

125 ml of methyl silicate, 400 ml of ethanol (abs.), 75 ml of H₂[O](distilled), 7.5 ml of acetic acid, and is diluted with 393 ml ofethanol (abs.) after a resting time of around 12 h.

The coating solutions for production of the oxides with intermediateindex of refraction are prepared by mixing the S and T solutions. Thelayer designated M in Example 1 is drawn from a dip solution with asilicon dioxide content of 5.5 g/l and a titanium dioxide content of 2.8g/l; the corresponding oxide contents of the M* dip solution are 11.0g/l and 8.5 g/l.

The wet chemistry sol-gel process used in Example 1, in the form of adip process, enables the economical coating of large surfaces such asarchitectural glass with interference filters, wherein the possibilityof coating both sides in a single work step and the production of mixedoxides with the particular desired index of refraction are of greatadvantage.

Panes can be coated either on both sides or, after covering one side ofthe glass, just on one side.

Alternative coating methods are physical vaporization in high vacuum andmodifications of this process in terms of ionic and plasma assistance,and cathode sputtering.

FIG. 4 shows the transmission spectrum of a filter according to theinvention in the wavelength range of 280 to 480 nm, made according toExample of embodiment 1 (color-neutral filter). Even without the use ofpolymer substances, the dangerous UV-B region is completely blocked, andthe UV-A region is more than ⅔ blocked, while only the less dangerousrange of 340-380 nm is around ⅓ transmitted. It should be noted that theharmfulness of UV radiation increases steadily toward shorterwavelengths.

The transmissibility in the wavelength range of 300 to 380 nm is 15%,which is a UV attenuation by a factor of 4 as compared to an uncoatedglass pane (around 60%). In the case of building glazings, however,double panes are usually employed, and less often triple panes. The useof multiple panes further improves the UV protection considerably, asFIG. 5 shows.

In the case of double panes, each provided with the UV filter accordingto the invention on both sides, the transmissibility in the range of300-380 nm is already reduced to 7%; for triple panes, a value of 4% hasbeen measured. At the same time, the reflection losses in the region ofvisible sunlight for these architectural glazings are only around 1% forsingle panes, and around 2% or 3% for double or triple panes,respectively. As compared to uncoated glasses, this signifies a 7%reduction of the reflection losses in absolute terms for the singlepane, and 14% and 21% for the double and triple panes, respectively.

Especially for glazings of museums and textile specialty shops, thiscreates a new state of the art, since the five-layer filter of theinvention represents only a relatively small additional expense comparedto the three-layer solution.

Furthermore, the filter according to the invention also solves theproblem of realizing at the same time a color-neutral antireflection,which also guarantees a color-neutral antireflection at rather largeviewing angles, thanks to the broad width of the range of lowreflection.

FIG. 6 shows the measured reflection characteristic of the filteraccording to the invention in the visible region of 380 to 780 nm as afunction of the viewing angle (12.5-50°). A comparison with FIGS. 1 and2 demonstrates the superiority of the solution according to theinvention as compared to MIROGARD and also AMIRAN in terms ofbroadbandedness, including in particular rather large viewing angles.This is also apparent from FIG. 7 by comparing the filter according tothe invention with these three-layer solutions for a given viewing angleof 30°.

FIGS. 8a and 8 b show the reflection spectrum for a viewing angle of 8°with different scales for R, and a wavelength range that is especiallyenlarged in the UV direction: the average degree of reflection in theregion of 400 to 800 nm is 1%, the subjective color impression isessentially more neutral, especially for large viewing angles above 30°,than is the case with all traditional three-layer antireflections.

As FIG. 8a shows, the blocking action of the UV filter according to theinvention is based primarily on reflection, and less on absorption (UVreflector). The thus-produced optical filters not only exhibit theabove-described wavelength-dependent transmission and reflectioncharacteristic, but also are distinguished in particular by a highoptical quality, they are free of cracks, opacities, and lightscattering, and provide a very color-neutral impression in reflection.Yet neither do they have any color-distorting effect in transmission,which is very important for picture glazings, for example.

The following service-life and application tests were carried out withfilters produced according to Example 1 with regard to an application ininterior rooms:

Boil test (DIN 51 165), water of condensation/constant climate (DIN 50017), salt spray/mist test (DIN 50 021), Cass test (copperchloride+acetic acid+NaCl)

and with regard to exterior application

Test for resistance to water of condensation, test for acid resistance,test for wear resistance (each time requirement category A).

The glasses coated according to the invention withstood the testsindicated here and can therefore be used both in interior spaces and inthe exterior field, for example, as architectural glazings.

The invention shall now be further explained by means of two additionalexamples of embodiment:

EXAMPLE 2

(Green Antireflection):

A UV filter with combined broadband antireflection action on soft glass,for the purpose of a green residual reflection color, is producedanalogously to Example 1, but the first layer (M*) of Example 1 is nowreplaced by a layer M# which is drawn from a mixed silicon/titaniumsolution of modified composition. This solution has a silicon dioxidecontent of 11.0 g/l and a titanium dioxide content of 5.5 g/l. Due tothe relatively low titanium content, the M# layers thus produced have asomewhat lower index of refraction than M*.

As the drawing speeds for the individual layers M#/TIM/T/S there are nowselected: v=540/262/345/206/500 mm/min., obtaining an optical filterwith a reflection characteristic according to FIG. 9, which differsessentially from the filter of Example 1 only in the altered residualreflection in the visible range. The other properties of the filtercorrespond to Example 1.

EXAMPLE 3

(Blue-violet Antireflection):

A filter according to the invention, but with blue-violet color of theresidual reflection, is produced by the method and also with theindividual layers of Example 1, but with the following drawing speedsfor M*/T/M/T/S: v=525/247/302/194/470 mm/min. In this way, a filter witha reflection characteristic according to FIG. 10 is obtained. The otherproperties of the filter except for the altered color impression of theresidual reflection correspond to those of Examples of embodiment 1 and2.

The invention for the first time specifies a coating which makes theglass/air interfaces antireflecting in the visible wavelength range(380-780 nm), preferably neutral in color, and at the same time itsubstantially improves the UV protection properties of transparentsubstrates in the wavelength range of UV-A (315-380 nm) and UV-B(280-315 nm).

Fields of application of the optical filters according to the invention,besides the coating of glass panes, are the coating of light bulbs inthe light industry in order to improve the emitted visible light withcolor neutrality, especially including that at rather large emissionangles, while at the same time reducing the UV radiation. This appliesespecially to gas discharge lamps with quartz glass bulbs, such as metalhalide bulbs, but also to a lesser extent to halogen lamps with quartzor hard glass bulbs.

Furthermore, tubular casings for lamps can be coated with the filteraccording to the invention, and the filter can be used on planar frontpanels of hard and soft glass.

An especially preferred usage of the interference layer systemsaccording to the invention is the coating of thermal protection glasses.

FIGS. 11a through 11 c represent application configurations ofUV-reflective thermal protection glasses according to the invention,wherein at least one side of a transparent substrate has been coatedwith a UV-reflective, interference system of five layers. Other layerstructures are also possible, as long as the individual layers containthe temperature-stable inorganic materials according to the invention.

FIG. 11a shows a simple system, a so-called single pane, comprising asubstrate 100, on whose side facing the interior of a space 102 has beendeposited a thermal protection layer, in the present case, a tin oxidelayer 104. On the outer side, the single pane comprises an interferencelayer system 106 according to the invention. With such a system, atransmission of more than 93% and a reflection of 2% in the visiblerange are achieved, and in the UV range the transmission is reduced toless than 8% of the incident light.

The achievable k-value is 3.5 W/m²K.

By using two transparent substrates 100.1, 100.2, it is possible toconstruct a double insulated glass pane, as shown in FIG. 11b. In thecase of the double insulated glass pane shown in FIG. 11b, only onetransparent substrate, the transparent substrate 100.1, is coated with aheat-reflecting tin oxide layer 104. The tin oxide layer 104 adjoins theinterior 108 of the double pane. On all four sides of the twotransparent substrates 100.1, 100.2, UV-reflective interference layersystems 106.1, 106.2, 106.3, 106.4 are deposited. With such a system, atransmission of more than 88% can be achieved with a reflection of lessthan 3% in the visible range. The transmission in the UV range is lessthan 4%, and the k-value is 1.6 W/m²K.

FIG. 11c, in turn, shows a system with two transparent substrates 100.1,100.2. The system is distinguished from the system of FIG. 11b in thatheat-reflecting layers 104.1, 104.2 are deposited on both transparentsubstrates 100.1, 100.2 on the inside 108 of the double insulated glasspane. As with the embodiment according to FIG. 11b, all sides of thetransparent substrates are coated with a 5-layer interference systemaccording to the invention.

In a system according to FIG. 11c, a transmission of more than 87% and areflection of less than 3% in the visible range are achieved. Thetransmission in the UV range is less than 3% and the k-value is 1.2W/m²K.

By UV region is meant primarily the wavelength region of 280 to 380 nm.The transparent substrate used is a non-iron-poor float glass substrateof 4 mm thickness.

In the case of the interference layer systems which are deposited on thethermal protection glass for broadband antireflection, the uppermost ofthe five layers (S) next to the air has an index of refraction which isless than that of glass (n=1.52). The layer consists preferably almostentirely of quartz glass (SiO₂, n=1.40-1.46). The second and fourthlayers (T)—viewing from S—consist of a material with a high index ofrefraction (n=2.0-2.3), preferably titanium dioxide (TiO₂). The M layershave an intermediate index of refraction of n=1.6-1.8, which can berealized preferably by a mixed silicon/titanium oxide.

The layer thickness of the M layer(s) next to the glass or tin oxide is70-100 nm, depending on the configuration of the optical filter, that ofthe other M layers is 20 to 40 nm, the T layer closer to the glass has alayer thickness of 30 to 70 nm, the T layer closer to S is 30 to 50 nm,and the cover layer (S) is 90 to 110 nm.

These materials are deposited on the glass substrate preferably by dipmethods, for example, it is possible to coat a flat glass pane either onboth sides or, after covering one side of the glass, just on one side.The thermal protection glasses obtained with the interference layersystem according to the invention shall now be explained more closely bymeans of examples of embodiment:

EXAMPLE 4

A plate glass coated on one side with tin oxide (d=3 mm, not iron-poor,surface resistance 15 Ohms) is provided on both sides identically with aUV-reflective 5-layer broadband antireflection coating by means of thedip method (sol-gel process) in keeping with Example 1 mentioned above,so that a structure STMTM/glass/tin oxide/MTMTS is formed.

The plate glass thus improved has a wavelength-dependent transmissionaccording to FIGS. 12a-12 c and a reflection characteristic (when thetin oxide side is illuminated) according to FIGS. 12d and 12 e. Thecoatings have a high optical quality and are free of cracks, visibleopacities, and light scattering.

One particular feature of the invention is the smoothing out of the tinoxide surface, which is relatively rough prior to the coating, thanks tothe 5-layer antireflection coating: while the uncoated tin oxide surfaceis characterized by roughness values ofR_(a)/R_(z)/R_(max)=0.02/0.30/0.52 μm, these values are reduced to0.02/0.08/0.10, by the antireflection coating, which corresponds to thevalues for uncoated float glass.

As cleaning tests show, this also makes possible an application of thetin oxide layer to the outside of glazings, and thus in the simplestinstance a single-pane thermal protection glazing, as shown in FIG. 11a.This is of special interest for exhibition halls, for which thus far itwas only possible to use single-pane glazings without a heat-reflectinglayer. But since the heat-reflection function is impaired by a coatingof water, the tin oxide side must be directed toward the interior of thebuilding.

FIG. 12c shows that, in the visible range, only a moderateantireflection action of around 1% is achieved with the coated glass 100according to the invention—as compared to fully uncoated float glass102—but the heat transfer coefficient is lowered from 5.8 W/m²K toaround 3.5 W/m²K, and thus approaches the k-value of an uncoatedinsulated glass double pane of around 3.0 W/m²K. The UV transmission(FIG. 12b) is lowered from 55% for uncoated float glass 102 or 40% forfloat glass with AMIRAN antireflection on both sides, to 8% (not shownin FIG. 12b).

As FIG. 12a shows, above a wavelength of around 2500 nm in the infraredthe optical properties of the tin oxide layer are not altered by theUV-reflective antireflection layers. In the intermediate range of thenear infrared (NIR, 780-2500 nm), a considerable sun protection actionis achieved as compared to uncoated K-glass 104, since the lowering ofthe transmission in the range of 1050 to 2400 nm significantly outweighsthe transmission gain in the range of 780-100 nm, both times weightedwith the incoming radiation spectrum of the sun.

The single pane coated with an interference layer system according tothe invention according to Example 4 can also be used to constructdouble-panel insulated glass.

The single pane according to Example 4, furthermore, can be used as anelectric heating panel, if the tin oxide layer is grounded as anantielectrostatic element, or for reflection of electromagnetic waves.

The following service-life and application tests according to DIN EN1096-2 have been carried out on the filter prepared according to Example1: testing for resistance to water of condensation, testing for acidresistance, testing for salt spray/mist (neutral), testing for wearresistance, each time requirement category A, and the requirement forarchitectural glazings has been fulfilled.

FIGS. 12d-e show the reflection curves for thermal protection glass 104as compared to thermal protection glass 104 coated with the interferencelayer system according to the invention.

Additional examples of embodiment for UV-reflective thermal protectionglass shall be specified below.

EXAMPLE 5

A plate glass coated on one side with tin oxide according to Example 4is provided with a modified 5-layer antireflection, thereby forming thestructure STMTM/glass/tin oxide/TMTS, which is equivalent to omittingthe thick M layer on the tin oxide side. This is achieved by firstgluing together two plate glasses at the edges by the tin oxide sides,then coating the combination with an M layer according to Example 4 bythe dip method, separating the panes, and then further coating each ofthem on both sides with the structure TMTS, all of this according toExample 4.

The UV-reflective thermal protection glass according to Example 5according to the invention has largely the same properties as thatproduced by Example 4; the major difference is an improved transmissionin the visible range of 92%, which is accomplished by a mean visiblereflection improved to 1.9%.

EXAMPLE 6

The method is the same as in Example 5, except that the drawing speed toproduce the T-layer closer to the glass is reduced from 262 mm/min. to220 mm/min., and thus the thickness of this layer is reduced by around11%. In this way, the mean visible residual reflection is furtherreduced to 1.5%, so that the visible transmission is further improved to93%, while the other properties are unchanged in comparison to Examples4 and 5.

As is apparent, for example from FIGS. 6, 7, 8 b, 9 and 10 as well asFIGS. 12b-e, the reflectivity of the interference layer system in thewavelength range of 300-380 nm is ≧20% and the reflectivity in thewavelength range of 450-800 nm is ≦5%.

What is claimed is:
 1. A UV-reflective interference layer system fortransparent substrates with broadband antireflection in the visiblewavelength range, the interference layer system comprising at least fiveindividual layers, wherein consecutive layers of the five individuallayers have different indices of refraction and the five individuallayers have UV and temperature-stable inorganic materials, characterizedin that the interference layer system has the following structure:substrate/M1/T1/M2/T2/S, wherein substrate designates the transparentsubstrate, M1, M2 denote layers with intermediate index of refraction,T1, T2 denote layers with high index of refraction, S denotes a layerwith low index of refraction, and for a reference wavelength of 550 nmthe indices of refraction of the individual layers lie in the followingrange: n _(low)≦1.6 1.6>n _(intermediate)<1.8 1.9≦n _(high)  and thethickness of the individual layers lies in the following range: for thelayer M1: 70 nm≦d_(M1)≦100 nm for the layer T1: 30 nm≦d_(T1)≦70 nm forthe layer M2: 20 nm≦d_(M2)≦40 nm for the layer T2: 30 nm≦d_(T2)≦50 nmfor the layer S: 90 nm≦d_(S)≦110 nm.
 2. The interference layer systemaccording to claim 1, wherein the inorganic materials are inorganicoxides.
 3. The interference layer system according to claim 1, whereinthe inorganic oxides are largely transparent above a wavelength of lightof 320 nm.
 4. The interference layer system according to claim 1,wherein the five individual layers comprise a material selected from thegroup consisting of TiO₂, Nb₂O₅, Ta₂O₅, CeO₂, HfO₂, SiO₂, MgF₂, Al₂O₃,ZrO₂, and any combinations thereof.
 5. The interference layer systemaccording to claim 1, wherein the five individual layers comprise thefollowing materials: the high-refracting layer with n_(high), TiO₂ thelow-refracting layer with n_(low), SiO₂ and the intermediate-refractinglayer with n_(intermediate), a mixture of TiO₂ and SiO₂.
 6. Theinterference layer system according to claim 1, wherein the T1, T2layers with n_(high) comprise one or more of the following materials:Nb₂O₅, Ta₂O₅, CeO₂, HfO₂, or mixtures of these with TiO2, the S layercomprise the following materials: MgF₂ or mixtures of MgF₂ with SiO₂,and the M₁, M₂ layers comprise one or more of the following materials:Al₂O₃, ZrO₂.
 7. The interference layer system according to claim 1,wherein the transparent substrate is soft glass.
 8. The interferencelayer system according to claim 1, wherein the transparent substrate isa hard glass.
 9. The interference layer system according to claim 1,wherein the transparent substrate is quartz glass.
 10. A UV-reflectivethermal protection glass, comprising at least one transparent substrate,wherein the substrate has a heat-reflecting coating on at least oneside, which has a surface resistance <20 Ω, wherein the substrate, whichhas a heat-reflecting coating on at least one side, has at least oneUV-reflective interference layer system disposed thereon, said at leastone UV-reflective interference layer system comprising at least fiveindividual layers in the following structure: M1/T1/M2/T2/S, wherein M1,M2 denote layers with intermediate index of refraction, T1, T2 denotelayers with high index of refraction, S denotes a layer with low indexof refraction, and for a reference wavelength of 550 nm the indices ofrefraction of the individual layers lie in the following range: n_(low)≦1.6 1.6>n _(intermediate)<1.8 1.9≦n _(high)  and the thickness ofthe individual layers lies in the following range: for the layer M1: 70nm≦d_(M1)≦100 nm for the layer T1: 30 nm≦d_(T1)≦70 nm for the layer M2:20 nm≦d_(M2)≦40 nm for the layer T2: 30 nm≦d_(T2)≦50 nm for the layer S:90 nm≦d_(S)≦110 nm.
 11. The UV-reflective thermal protection glassaccording to claim 10, wherein the UV-reflective interference layersystem is deposited onto the heat reflecting interference layer system.12. The UV-reflective thermal protection glass according to claim 10,wherein the UV-reflective interference layer system is depositeddirectly on the substrate, and a heat-reflecting layer with a surfaceresistance <20 Ω is deposited on the UV-reflective interference layer.13. The UV-reflective thermal protection glass according to claim 10,wherein the UV transmission of the thermal protection glass in the UVrange of 280-380 nm is less than 8% and in the visible wavelength rangeit is greater than 90%.
 14. The UV-reflective thermal protection glassaccording to claim 10, wherein the heat-reflecting coating comprises oneor more of the following materials: SnO₂:F,Sb ZnO:Al In₂O₃:Sn Ag-basedcoating.
 15. The UV-reflective thermal protection glass according toclaim 10, wherein the heat transfer value of the thermal protectionglass is smaller than 3.5 W/m²K.
 16. The UV-reflective thermalprotection glass according to claim 10, wherein the UV thermalprotection glass comprises two transparent substrates yielding adouble-pane insulated glass, wherein at least one side of one of thetransparent substrates has a heat-reflecting layer and at least threesides of the two substrates comprise the reflective interference layersystem.
 17. The UV-reflective thermal protection glass according toclaim 16, wherein the double-pane insulated glass has a small k-value ofless than 1.0 W/m²K, a UV transmission of less than 4%, and a visibletransmission in the visible wavelength range of greater than 85%.
 18. AUV-reflective interference layer system for a transparent substrate,comprising: a first layer disposed on the transparent substrate, saidfirst layer having an intermediate index of refraction; a second layerdisposed on said first layer, said second layer having a high index ofrefraction; a third layer disposed on said second layer, said thirdlayer having said intermediate index of refraction; a fourth layerdisposed on said third layer, said fourth layer having said high indexof refraction; and a fifth layer disposed on said fourth layer, saidfifth layer having a low index of refraction, said first through fifthlayers combining to transmit less than 8% of light having an UVwavelength while transmitting greater than 90% of light having a visiblewavelength.
 19. The UV-reflective interference layer system as in claim18, wherein said intermediate index of refraction is between about 1.6and about 1.8 for a reference wavelength of 550 nm, said high index ofrefraction of greater than or equal to 1.9 for said referencewavelength, and said low index of refraction of less than or equal to1.6.
 20. The UV-reflective interference layer system as in claim 18,wherein the transparent substrate is glass selected from the groupconsisting of a hard glass, a soft glass, and quartz glass.
 21. TheUV-reflective interference layer system as in claim 18, furthercomprising a heat-reflecting coating disposed either on said fifth layeror between the transparent substrate and said first layer.
 22. TheUV-reflective interference layer system as in claim 18, wherein saidheat-reflecting coating provides a heat transfer value less than 3.5W/m²K.
 23. The UV-reflective interference layer system as in claim 18,wherein said first through fifth layers combine to provide broadbandantireflection at a viewing angle in a range of between 12.5 degrees toabout 50 degrees.